Process and solution for fixing an image on silver halide prints

ABSTRACT

A rapid process for producing a stable visible image in a photographic silver halide emulsion layer containing a latent image which comprises developing the layer in a photographic silver halide developing solution and fixing the silver halide forming the resultant image by immersing the layer in a novel fixing solution. The novel fixing solution has a major proportion of a solution including a first compound selected from the group consisting of alkali metal thiocyanate, ammonium thiocyanate, alkali metal thiosulfate, and ammonium thiosulfate, and a minor proportion of a second solution including an anionic synthetic detergent having a carbon chain length in the range of between about 7 to about 18 carbon atoms per molecule and selected from the group consisting of ammonium lauryl sulfate sodium lauryl sulfate, potassium lauryl sulfate, aklylated aromatic sulfonic acids, and mixtures thereof; and a water softening agent selected from the group consisting of sodium hexametaphosphate sodium pyrophosphate, sodium tetraphosphate, and mixtures thereof. The resultant image layer is subsequently rinsed in a moving water bath.

United States Patent [191 Ritchey [451 Dec. 17, 1974 Edward R. Ritchey, 303 S. 5th St., St. Joseph, Mo. 64501 [22] Filed: May 16, 1973 [21] Appl. No.: 360,652

[76] Inventor:

[52] U.S. Cl. 96/61 R, 96/50 R [51] Int. Cl G03c 5/38, G03c 5/26 [58] Field of Search 96/50 R, 61 R [5 6] References Cited UNITED STATES PATENTS 2.343,696 3/1944 Muehler et a1 961/61 R 2,578,075 12/1951 Kienast 96/61 R 2,860,978 11/1958 Henn et a1. l 96/61 R 3.132.943 5/1964 Smith et a1 96/61 R 3.404004 10/1968 Ake t 96/50 3,573,912 4/1971 Brown 96/61 R Primary Examiner-Mary F. Kelley Attorney, Agent, or FirmJohn H. Widdowson [5 7] ABSTRACT A rapid process for producing a stable visible image in a photographic silver halide emulsion layer containing a latent image which comprises developing the layer in a photographic silver halide developing solution and fixing the silver halide forming the resultant image by immersing the layer in a novel fixing solution. The novel fixing solution has a major proportion of a solution including a first compound selected from the group consisting of alkali metal thiocyanate, ammonium thiocyanate, alkali metal thiosulfate, and ammonium thiosulfate, and a minor proportion of a second solution including an anionic synthetic detergent having a carbon chain length in the range of between about 7 to about 18 carbon atoms per molecule and selected from the group consisting of ammonium lauryl sulfate sodium lauryl sulfate, potassium lauryl sulfate, aklylated aromatic sulfonic acids, and mixtures thereof; and a water softening agent selected from the group consisting of sodium hexametaphosphate sodium pyrophosphate, sodium tetraphosphate, and mixtures thereof. The resultant image layer is subsequently rinsed in a moving water bath.

30 Claims, No Drawings PROCESS AND SOLUTION FOR FIXING AN IMAGE ON SILVER HALIDE PRINTS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to photography. Most specifically, this invention provides a rapid process for producing a stable visible image in a photographic silver halide emulsion layer containing a latent image, and a novel fixing solution for use therein.

2. Description of the Prior Art It is generally old in the art of producing a stable visible image and photographic silver halide emulsion layer containing a latent image formed therein by exposure to light in a camera, enlarger, X-ray machine, or similar apparatuses, to develop the silver halide layer in a developing solution, to stop the developing action of the developer solution, to fix the silver halide forming the resultant image by immersing the layer in a stabilizing solution, and to subsequently rinse the resultant photographic image layer in a moving water bath. This process has been disclosed by Richard W. Henri et al in US. Pat. No. 2,860,978, patented Nov. 18, 1958,

' Eric T. Smith et al in US. Pat. No. 3,132,943, patented May 12, 1964, and in Ake US. Pat. No. 3,404,004, patented Oct. l, 1968. Prior to Ake patent, it was common subsequent to fixing to go through an extensive and time consuming washing operation taking approximately from 30 minutes to 60 minutes in order to remove all fixing chemicals from the plate or print. The removal of these fixing chemicals and soluble byproducts of the fixing operation is necessary in order to prevent deterioration of the print, film, or plate caused from residual thiosulfate or thiocyanate solutions converting part of the silver image into a yellowish or brownish silver sulfide. This extensive washing could be shortened to approximately 3 minutes, followed by immersion into a running water bath for minutes. Even the inclusion of the hypo eliminator step and subsequent washing should be followed by another bath operation for flattening the print or plate; which should still yet be followed by still another bath to provide for treatment prior to handling the plate or print on an enlarging machine, orsimilar apparatus, and in toning operations. The time consuming washing operation following the hypo eliminator step normally takes from between to 35 minutes. Conventional processes after the hypo treatment require a minimum of four washing operations, baths, or solutions, and the equipment form handling the same. Notwithstanding this rigorous extensive and time consuming washing, frequently a portion of the chemicals used to process the print or plate still remain and decompose to cause staining.

Ake US. Pat. No. 3,404,004, discloses a new rapid process and a final soak bath used therein for producing a stable image in a photographic layer containing a latent image which solved many of the foregoing problems associated with developing processes known to the prior art. This patented rapid process includes the steps of 1) developing the layer in a developing solution; (2) stopping the action of the developing solution; (3) fixing the resultant image in a stabilizing solution; and (4) treating the layer in the final soak bath for removing chemical residue. Following the last step, the resultant image is rinsed in a moving water bath for a time interval in a range of about 4 to 7 minutes. The

process completely cleared the photographic layer of all chemical residue in minimul time with a single soak, and simultaneously to soaking the process provided a flattening treatment. However, this patented process did not curtail the time for fixing the silver halide forming the resultant latent image by immersing the layer in a thiosulfate or thiocyanate solution; nor could this process eliminatethe step of stopping the action of the developing solution by immersing the layer in an acetic acid solution.

Therefore, what is needed and what has been invented by me since Oct. 1, I968, the date which Ake US. Pat. No. 3,404,004 issued, is a novel process and a new fixing solution which is to be used therein, which produces a stable visible image in a photographic silver halide emulsion layer containing a latent image without the foregoing deficienciess associated with the prior art.

SUMMARY OF THE INVENTION It is therefore an object of this invention to provide a novel process and fixing solution for producing a stable visible image in a photographic silver halide emulsion layer containing a latent image which includes a shorter fixing time with archival permanence.

It is another object of this invention to provide a novel process and fixing solution for producing a stable visible image in a photographic silver halide emulsion layer containing a latent image which requires no stop bath and gives no darkroom odors.

It is yet another object of this invention to provide a new photographic processing method and a non-toxic, biodegradable fixing solution wherein there is less wash time and is relatively economical to manufacture and install in known apparatuses and processes.

Still, other objects will be apparent to those skilled in the art from the following description of this invention.

The foregoing objects were achieved according to the practice of this invention. Broadly, this invention comprises an improved rapid process for producing a stable visible image in a photographic silver halide emulsion layer containing a latent image which includes developing the layer in a photographic silver halide developing solution. Subsequent to developing, the silver halide forming the resultant latent image is fixed by immersing the layer in a novel fixing solution having a major proportion of a solution including a first compound selected from the group consisting of alkali metal thiocyanate, ammonium thiocyanate, alkali metal thiosulfate and ammonium thiosulfate. The novel fixing solution additionally includes a minor proportion of a second solution including an anionic synthetic detergent having a carbon chain length in the range of be tween about 7 to about 18 carbon atoms per molecule and selected from the group consisting of ammonium lauryl sulfate, sodium lauryl sulfate, potassium lauryl sulfate, alkylated aromatic sulphonic acids, and mixtures thereof; and a water softening agent selected from the group consisting of sodium hexametaphosphate, sodium pyrophosphate, sodium tetraphosphate, and mixtures thereof. The second solution preferably additionally includes a print flattening agent selected from the group consisting of propylene glycol, hexylene glycol, ethylene glycol, glycerol, and mixtures thereof; and a defoaming agent selected fromthe group consisting of methylhexacarbonyl sulfonated ores, sulfonated silicones, and mixtures thereof. Following fixing, the resultant image layer is rinsed in a moving water bath.

Thus, by the practice of this invention, there is provided a rapid and economical process for producing a stable visible image in a photographic silver halide emulsion layer containing a latent image, and a novel fixing solution which is used within the process.

Detailed Description of the Invention In the new rapid process of my invention, the photo graphic print, X-ray, plates, negatives, or other photographic elements are initially placed in a silver halide developing solution. The photographic elements in general have a silver halide emulsion layer containing a latent image. The latent image is formed in the emulsion layer by exposure to light in a camera, enlarger, X-ray machine, or similar apparatus. The developer bath can be of any suitable type known to the prior art, as for example, a mild reducing agent such as pyrogallic acid. If the photographic eiernents are multilayer photographic film, paper, etc., used for color photography containing three or more selectively sensitive emulsion layers coated on a photographic support and possibly including color forming compounds or couplers, the developer bath or baths will be selected to develop the respective type of film or photographic element.

After the photographic element has been removed from the developer bath, or baths,.it is either immersed directly into my novel fixing solution, or it is immersed in a solution for stopping the action of the developer solution prior to immersing the photographic element into the new fixing solution. The choice of steps will hereinafter follow as the description and proceeds depends upon certain concentrations of certain solutions within my fixing solution which comprises a major proportion of a first solution including a first fixing agent compound selected from the group consisting of alkali metal thiocyanate, ammonium thiocyanate, alkali metal thiosulfate, and ammonium thiosulfate. The alkali metal thiocyanate may be selected from the group consisting of lithium thiocyanate, sodium thiocyanate, potassium thiocyanate, rubidium thiocyanate, and cesium thiocyanate, and the alkali metal thiosulfate may be selected from the group consisting of lithium thio' sulfate, sodium thiosulfate, potassium thiosulfate. rubidium thiosulfate. and cesium thiosulfate. if an alkaline fixing solution is desired, the first solution should additionally include desiccated alkali metal sulfite or desiccated ammonium sulfite, alkali metal bisulfite or ammonium bisulfite and water. The desiccated alkali metal sulfite may be selected from the group consisting of desiccated lithium sulfite, sodium sulfite, potassium sulfite, rubidium sulfite, and cesium sulfite. Similarly, the alkali metal bisulfite may be selected from the group consisting of lithium bisulfite, sodium bisulfite, potassium bisulfite, rubidium bisulfite, and cesium bisulfite. However, the first fixing agent is normally used in an acid solution instead of an alkaline fixing solution because the acid stops developing as quickly as it diffuses into the film, and it also prevents oxygen oxidation of the developing agent with the attendant possibility of stain formation. Thus, if an acid hardening bath is desired in place of the alkaline non-hardening bath, then a quantity of acetic acid, crystals of boric acid, and potassium alum or chrome alum may be substituted for the alkali metal bisulfite or ammonium bisulfite. The acetic acid is preferably 28% pure acetic acid made from glacial acetic acid which has been diluted with water in a ratio of about three parts of glacial acetic acid with eight parts of water. Crystalline boric acid should be used instead of powdered boric acid because the powdered acid dissolves only with great difficulty.

if an alkaline non-hardening-bath is desired, the first fixing agent compound should have a concentration in the range of between about 145 to about 175 grams per liter of water; the desiccated alkali metal sulfite or ammonium sulfite should include a concentration in the range of between about 4 to about 9 grams per liter of water; and the alkali metal bisulfite or ammonium bisulfite should possess a concentration in the range of between about 12 to about 21 grams per liter of water. If the acid hardening bath is desired, then first solution should contain the first fixing agent with a concentration in the range of between about 135 to about 160 grams per liter of water; the desiccated alkali metal sulfite or ammonium sulfite in a concentration range of between about 5 to about 15 grams per liter of water; the glacial acetic acid ina concentration range of between about 20 cc to about cc per liter of water wherein every three parts of the glacial acetic acid has been initially diluted with eight parts of water; crystals of boric acid having a concentration range of between about 1 gram to about 10 grams per liter of water; and potassium or chrome alum including a concentration range of between about 5 grams to about 15 grams per liter of water. In the preferred embodiment of the invention, a non-hardening bath of the first solution comprises l60 grams .of sodium thiosulfate per liter of water, about 6.6 grams of desiccated sodium sulfite per liter of water, and about 16.7 grams of sodium bisulfite per liter of water. The preferred embodiment of the acid hardening bath of the first solution comprises about 147.5 grams of sodium thiosulfate per liter of water, about 9.25 grams of sodium sulfite per liter of water, about 29.2 grams of 28% pure acetic acid per liter of water, about 4.62 grams of crystazls of boric acid per liter of water, and about 9.25 grams of potassium or chrome alum per liter of water.

The novel fixing solution additonally includes a minor portion of a second solution including an anionic synthetic detergent having a carbon chain length in a range of between about 7 to about 18 carbon atoms per molecule and selected from the group consisting of ammonium lauryl sulfate, sodium lauryl sulfate, potassium lauryl sulfate, alkylated aromatic sulfonic acid, and mixtures thereof, and a water softening agent selected from the group consisting of sodium hexametaphosphate, sodium pyrophosphate, sodium tetraphosphate and mixtures thereof. Preferably, the second solution additionally includes a print flattening agent selected from the group consisting ofpropylene glycol, hexylene glycol, ethylene glycol, glycerol, and mixtures thereof; and a defoaming agent selected from the group consisting of methylhexacarbonyl, sulfonated ores, sulfonated silicones and mixtures thereof.

The detergent agent used in my second solution may be any suitable type of the detergent. By detergent it is meant a compound having a molecule characterized as a relatively large hydro carbon molecule having from 7 to 18 carbon atoms, usually aliphatic or alkyl substituted aromatics in nature. One portion of the molecule is water soluble and posesses a relatively high polarity. This is the hydrophilic or solubilizing group. Typical solubilizing groups are COOH, -SO H, and SO HR The most preferred detergent for use in the practice of my invention is ammonium lauryl sulfate sold under the trademark SIPON L22 by Alcolac Chemical Corporation. The detergent agent, preferably ammonium lauryl sulfate, can be used in any suitable concentration in the second solution. However, I prefer to use the detergent in a concentration range of between about 0.002 to about 0.02 grams per liter, more preferably a concentration in the range of about 0.006 to about 0.007 grams per liter.

Any suitable water softening agent can be used in the second solution of my invention. The preferred water softening agent for use in the second solution of my invention is hexametaphosphate, sold under the trademark Calgon by Calgon Corporation, and fully described in US. Pat. No. 2,494,828. The water softening agent, preferably hexametaphosphate, can be used in any suitable concentration in the second solution of my invention. Preferably, the water softening agent is used in a concentration range of between about 0.01 to about 0.15 grams per liter; more preferably, in the range of between about 0.02 to about 0.03 grams per liter; and most preferably, a concentration of about 0.022 grams per liter.

A print flattening agent may be included in the second solution of my invention. It is preferred that the print flattening agent by propylene glycol and used in the aqueous solution in any suitable concentration; preferably in the range of between about 2.6 X to about 65 X 10 gram moles per liter; more preferably, in a concentration range of between about 4.8 X 10 to about 9.5 X 10 gram moles per liter. A suitable defoaming agent may also be used in the second solution in the practice of my invention. The preferred defoaming agent used in the second solution of my invention is 2 octanol. Another preferred defoaming agent is a sulfonated silicone mixture sold under the tradmark Antifoam B by Dow Corning Corporation. The defoaming agent, preferably 2-octanol, may be used in any suitable concentration. Preferably, the concentration is in the range of between about 0.7 X 10 to about 23 X 10' gram moles per liter; more preferably, the concentration is in range of between about 2.7 X 10 to about 5.6 X 10' gram moles per liter.

The second solution and the first solution may be mixed in any suitable concentration. Preferably, the second solution is mixed at a ratio of between about 1 ounce to about ounces of the second solution to about 1 gallon to the first solution. More preferably, the mixture ratio is between about 2 ounces to about 12 ounces of the second solution to about 1 gallon of the first solution; and most preferably, the mixing ratio is between about 4 ounces to about 6 ounces of the second solution to about 1 gallon of the first solution.

The photographic silver halide emulsion layer containing a latent image should be immersed in the novel fixing solution from between about 1 minute to about 5 minutes; preferably, for about 2 minutes. After immersion in the fixing solution, the photographic silver halide emulsion layer should be rinsed in a moving water bath from between about 1 minute to about 20 minutes, preferably for about 5 minutes; and subsequently dried in a normal manner which is well known to those skilled in the art.

As was previously mentioned, the photographic silver halide emulsion layer containing a latent image may be sent directly to fixing after the'developing without having to be immersedin a short solution. It has been discovered that if between about 1 and 5 ounces of the second solution is used with about 1 gallon of a working solution (that which includes water) of the first solutioii, then after developing the photographic silver halide emulsion layer may be directly immersed for about 2 minutes in the fixing solution without having to be initially immersed in a short-stop solution. If more than about 5 ounces of the second solution concentrate (that which is without water) is used with about 1 gallonpf a working solution of the first solution, then after developing and in accordance with the procedures which are well known to those skilled in the art, the print, plate or paper, should be placed in a short-stop acid solution. The short-stop acid solution includes a dilute solution of acetic acid having approximately between about 0.2% to about 0.8% of acetic acid, prefer ably about 0.5% of acetic acid. The immersion of the photographic silver halide layer in the short-stop solution should be from between about 15 seconds to about 45 seconds, preferably 30 seconds. i have also discovered that a working solution of my second solution may be substituted for the short-stop acid solution. If a working solution of my second solution is substituted for the short-stop acid solution to stop the developing action, then the photographic silver halide emulsion layer should be immersed in my second solution from between about 15 seconds to about 45 seconds, and preferably for about 30 seconds.

in the following is set forth examples of my invention which are given by way of illustration and not by limitation. The specific concentrations, temperatures, times, compounds, etc. set forth in these examples are not to be construed to unduly limit the scope of the invention.

EXAMPLE 1 Four double weight thickness photographic papers having a single halide emulsion layer thereon, were exposed to produce a latent image thereon. The papers were then developed in a conventional silver halide developing solution. After the papers were removed from the developing solution, the developing action of the developing solution was stopped by immersing the papers in an acetic acid solution. Each of the four photographic papers were subsequently fixed by a different method.

Method 1 took one of the four-photographic papers and immersed it in a well known fixing solution of sodium thiosulfate hypo sold by Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey. After five minutes of being immersed in this fixing solution, the paper was washed in a running water whose temperature was 68F.

Method ll took another paper and following a five minute fixation within the same fixing solution of Method I, soaked the paper for about 3 minutes in a Kodak hypo eliminator. After the immersion within this eliminator solution, the paper was washed in a running water bath having a temperature of about 68F. The hypo eliminator had the following composition:

Water 500c.c. Hydrogen Peroxide (3% solution) 125.0 c.c. Ammonia (3% solution) 100.0 c.c. Water to dilute 1.0 liter The hydrogen peroxide was initially dissolved in 500 cc of water and then the remaining chemical, ammonia, was added, taking care that the hydrogen peroxide was dissolved before adding the ammonia subsequently, water to dilute was added to the required volume.

Method Ill took a third paper and after fixation with the same fixing solution of Method I which is well known to those skilled in the art, soaked the paper in the novel bath solution of Ake US. Pat. No. 3,404,004 having a concentration of about four ounces of the consumer concentrate (i.e. 4 ounces of the concentrate solution per about 1 gallon of water) per about one gallon of water. This concentration of composition of the novel bath solution was clearly disclosed in Ake patent. After about a two minute soak in this bath solution, the paper was washed in a running water which had a temperature of about 68F.

Method IV took the last and fourth paper and fixed a stable visible image with the novel fixing solution of this invention. The fixing solution had a mixture ratio of about 4 ounces of the consumer concentrate of the second solution to about I gallon of a working solution of the first solution which had the following composition:

Water 6.5 liters Sodium Thiosulfate 147.5 grams/liter of H Desiccated Sodium Sulfate 9.25 grams/liter of H 0 Acetic Acid (28% pure) 29.2 grams/liter of H 0 Crystals of Boric Acid 4.62 grams/liter of H 0 Potassium Alum 9.25 grams/liter of H 0 Ammonium lauryl sulfate 0.85 ounces Propylene glycol 0.05 ounces Antifoam B (Dow Corning Corporation) 0.10 ounces Sodium hexametaphosphate (Calgon, Calgon Corporation) 3.0 ounces Four ounces of the concentrate solution was then combined with water to make a gallon of a consumer concentrate.

Following a five minute submersion of the fourth paper within my fixing solution, it was washed in running water having a temperature of about 68F.

All four methods washed the paper for about 60 minutes and took sodium thiosulfate measurements at 3, 6,

l0, I5, 25 and 60 minutes. The apparatus used for these measurements is well known to those in the art and was five-dram vials with polyethylene caps and a Carey Spectrophotometer. Table I gives the quantitative results of the residual hypo (sodium thiosulfate) measured in mg/cm as the aforementioned times for each method.

TABLE I WASH TIME RESIDUAL I-IYPO IN mg/cm FOR EACH IN MINUTES METHOD I II III IV too high to 3 measure 4.5 3.3 3.3 6 6.l 3.4 3.] 5.5 10 4.2 3.3 2.6 1.0 15 4.0 3.1 2.5 0.9 25 3.3 2.4 2.3 0.5 60 1.4 1.0 0.6 0.4

From the results of Table I, Method 1 illustrates that removal of residual hypo by simple washing was discouragingly slow and consequently, Method I cannot possibly be considered as an effective procedure for hypo elimination from paper based emulsions. Methods II and III produce almost parallel results. In each case, residual hypo content was reduced to reasonable limits within comparable times. Therefore, the choice of eliminators between the one used in Method II and the one in Method III cannot be made on the basis of hypo removal rates. Both were effective with Method III being the most effective after a certain specific time. Method IV was the process where my novel fixing solution was used and is clearly the method of choice because the paper was fixed and effectively free of residual hypo. Within 10 minutes after fixing the hypo level was reduced to archivial limits (1.0 mglcm No eliminator bath prior to washing was necessary to accelerate the washing time. Also, there were no deleterious effects resulting from mixing of the first solution with the second solution.

- EXAMPLE ,II

Method IV of Example I has a short-stop solution for stopping the developing of the conventional silver halide developing solution which consist of the chemical composition of the second solution of Example I. When EXAMPLE III A non-hardening alkaline first fixing solution has the following composition:

Water 1.5 Liters Sodium thiosulfate I60 grams/liter of H 0 Desiccated Sodium sulfite 6.6 7grams/liter of H 0 Sodium bisulfite l6. grams/liter of H 0 About 0.5 liters of water having a temperature of about l25F is used to initially dissolve the sodium thiosulfate. The remaining chemicals are dissolved in order given, taking care that each is completely dissolved prior to adding the next. The remaining about 1.0 liters of water was finally added to dilute the first solution to a working condition.

The second solution has the same chemical composition as the one given in Example I. However, in this example, only about 4 ounces of the consumer concentrate of the second solution are used with about 1 gallon of the first alkaline fixing solution. No short-stop solution is used to stop the developing action and the photographic paper is directly submerged from the developing step into the fixing solution of this example. After about 2 minutes of immersion, measurements of residual hypo are taken at the specific times of Table I. After 60 minutes of washing, the residual hypo measurements are similar to the measurements of Method IV and further illustrate that my novel manner of fixing can eliminate hypo faster than any process known to the prior art.

The foregoing examples illustrate that the new rapid process and novel fixing solution for processing photographic prints of my invention take considerably less time and favorable results are obtained. Upon completion of the example, it was determined that the papers were in perfect condition for toning operation. Also, the prints exhibited no apparent tendency to curl and showed less tendency to stain after drying.

While the present invention has been described herein with reference to particular embodiments thereof, and specific examples, a latitude of modifications, various changes and substitutions are intended in the foregoing disclosure, and in some instances some features of the invention will be employed without a corresponding use of other features without departing from the scope of the invention as set forth.

I claim:

l. A rapid process for producing a stable visible image in a photographic silver halide emulsion layer containing a latent image,

a. developing said layer in a photographic silver halide developing solution,

b. fixing said silver halide forming the resultant image by immersing said layer in a fixing solution having a major proportion of, (l) a first solution comprising a compound selected from the group consisting of alkali metal thiocyanate, ammonium thiocyanate, alkali metal thiosulfate and ammonium thiosulfate, and, (2) a minor proportion of a second solution including an anionic synthetic detergent having a carbon chain length in the range of about 7 to about l8 carbon atoms per molecule and selected from the group consisting of ammonium lauryl sulfate, sodium lauryl sulfate, potassium lauryl sulfate, alkylated aromatic sulfonic acids, and mixtures thereof, and a water softening agent selected from the group consisting of sodium hexametaphosphate, sodium pyrophosphate, sodium tetraphosphate, and mixtures thereof, wherein said second solution and said first solution are mixed at a ratio of between about 1 ounce to about 20 ounces of said second solution to about 1 gallon of said first solution, and

c. rinsing the resultant image layer in a moving water bath.

2. The rapid process of claim 1 additionally including immersing said layer in a developing stop solution after developing and prior to said fixing.

3. The rapid process of claim 1 wherein said second solution additionally includes a print flattening agent selected from the group consisting of propylene glycol, hexylene glycol, ethylene glycol, glycerol, and mixtures thereof, and a defoaming agent selected from the group consisting of methylhexacarbonyl, sulfonated oils, sulfonated silicones, and mixtures thereof.

4. The rapid process of claim 1 wherein said anionic synthetic detergent includes a concentration between about 0.002 to about 0.02 grams per liter, and said water softening agent includes a concentration in the range of between about 0.01 to about 0.15 grams per liter.

5. The rapid process of claim 3 wherein said print flattening agent includes a concentration between about 2.6 X 10 to about 65 X 10 gram moles per liter, and said defoaming agent includes a concentration range of between about 0.7 X 10 to about 23 X 10 gram mole per liter.

6. The rapid process of claim 1 wherein said immersing of said layer in said fixing solution is between about 1 minute to about 5 minutes, and said rinsing of said resultant image in a moving water bath is between about 2 minutes to about 20 minutes.

7. The rapid process of claim 1 wherein said alkali metal thiocyanate is selected from the group consisting of lithium thiocyanate, sodium thiocyanate potassium thiocyanate, rubidium thiocyanate, and cesium thiocyanate and said alkali metal thiosulfate is selected from the group lithium thiosulfate, sodium thiosulfate, potassium thiosulfate, rubidium thiosulfate, and cesium thiosulfate.

8. The rapid process of claim 2 wherein said developing stop solution is a dilute solution of acetic acid including approximately between about 0.2% to about 0.8% of acetic acid, and said immersing of said layer is from between about 15 seconds to about 45 seconds.

9. The rapid process of claim 2 wherein said developing stop solution is of the composition of said second solution and said immersing of said layer in said developing stop solution is from between about 15 seconds to about 45 seconds.

10. The rapid process of claim 7 wherein said first solution additionally includes desiccated alkali metal sulfite, alkali metal bisulfite and water.

11. The rapid process of claim 10 wherein said desiccated alkali metal sulfite is selected from the group consisting of lithium sulfite, sodium sulfite, potassium sulfite, rubidium sulfite, and cesium sulfite and mixtures thereof, and said alkali metal bisulfite is selected from the group consisting of lithium bisulfite, sodium bisulfite, potassium bisulfite, rubidium bisulfite and cesium bisulfite, and mixtures thereof.

12. The rapid process of claim 11 wherein a quantity of acetic acid, crystals of boric acid and potassium alum are substituted for said alkali metal bisulfite.

13. The rapid process of claiml wherein said first solution comprises water, between about to about grams per liter of water of a thiosulfate solution selected from the group consisting of alkali metal thiosulfate and ammonium thiosulfate, and a desiccated sulfite solution selected from the group consisting of alkali metal sulfite and ammonium sulfite having a concentration in the range of between about 5 to about 15 grams per liter of water, a glacial acetic acid in a concentration range of between about 20 cc to about 40 cc per liter of water wherein every three parts of said glacial acetic acid has been initially diluted with eight parts of water, crystals of boric acid having a concentration range of between about 1 gram to about 10 grams per liter of water, and potassium alum including a concentration range of between about 5 grams to about 15 grams per liter of water.

14. The rapid process of claim 3 wherein said first solution comprises water, about l47.5 grams of sodium thiosulfate per liter of water, desiccated sodium sulfite in a concentration of about 9.25 grams per liter of water, said glacial acetic acid having a concentration of about 29.2 grams per liter of water, said crystals of boric acid having a concentration of about 4.62 grams per liter of water, and said potassium alum having a concentration of about 9.25 grams per liter of water.

15. The rapid process. of claim 12 wherein chrome alum is substituted for said potassium alum.

16. The rapid process of claim 10 wherein said first solution comprises water, a thiosulfate solution selected from the group consisting of alkali metal thiosulfate and ammonium thiosulfate and in a concentration range of between about 145 to about 1 75 grams per liter, a desiccated sulfite solution selected from the group consisting of an alkali metal sulfite and ammonium sulfite and in a concentration range of between about 4 to about 9 grams per liter of water, and a bisulfite solution selected from the group consisting of an alkali metal bisulfite and ammonium bisulfite in a concentration range of between about 12 to about 21 grams per liter of water.

17. The rapid process of claim 16 wherein said first solution comprises water, sodium thiosulfate in a concentration of about 160 grams per liter of water, desiccated sodium sulfite in a concentration of about 616 grams per liter of water, and sodium bisulfite having a concentration of about 16.7 grams per liter of water.

18. A fixing solution for fixing a stable visible image on a developed photographic silver halide emulsion layer, comprising:

a. a major proportion of a first solution including a first compound selected from the group consisting of alkali metal thiocyanate, ammonium thiocyanate, alkali metal thiosulfate and ammonium thiosulfate, and

b. a minor proportion of a second solution including an anionic synthetic detergent having a carbon chain length in the range of between about 7 to about 18 carbon atoms per molecule and selected from the group consisting of ammonium lauryl sulfate, sodium lauryl sulfate, and potassium lauryl sulfate, alkylated aromatic sulfonic acids, and mixtures thereof, and a water softening agent selected from sodium hexametaphosphate, sodium pyrophosphate, sodium tetraphosphate, and mixtures thereof, wherein said second solution and said first solution are mixed at a ratio of between about 1 ounce to about 20 ounces of said second. solution to about 1 gallon of said first solution.

19. The fixing solution of claim 18 wherein said second solution additionally includes a print flattening agent selected from the group consisting of propylene glycol, hexylene glycol, ethylene glycol, glycerol, and mixtures thereof, and a defoaming agent selected from the group consisting of methylhexacarbonyl, sulfonated oils, sulfonated silicones and mixtures thereof.

20. A fixing solution of claim 18 wherein said anionic synthetic detergent includes a concentration in the range of between about 0.002 to about 0.02 grams per liter, and said water softening agent includes a concentration in the, range of between about 0.01 to about 0.l grams per liter. 1

21. The fixing solution of claim 19 wherein said print flattening agent includes a concentration in the range of between about 2.6 X to about 65 X 10' gram moles per liter, and said defoaming agent includes a concentration in the range of about 0.7 X 10' to about 23 X 10' gram moles per liter.

22. The fixing solution of claim 18 wherein said alkali metal thiocyanate is selected from the group consisting of lithium thiocyanate, sodium thiocyanate, potassium thiocyanate, rubidium thiocyanate, and cesium thiocyanate, and mixtures thereof, and said alkali metal thiosulfate is selected from the group consisting of lithium thiosulfate, sodium thiosulfate, potassium thiosulfate, rubidium thiosulfate and cesium thiosulfate, and mixtures thereof.

23. The fixing solution of claim 22 wherein said first solution additionally includes a desiccated sulfite solution selected from the group consisting of an alkali metal sulfite and ammonium sulfite, and a bisulfite solution selected from the group consisting of an alkali metal bisulfite and ammonium bisulfite.

24. The fixing solution of claim 23 wherein said desiccated alkali metal sulfite is selected from the group consisting of lithium sulfite', sodium sulfite, potassium sulfite, rubidium sulfite and cesium sulfite and mixtures thereof, and said alkali metal bisulfite is selected from the group consisting of lithium bisulfite, sodium bisulfite, potassium bisulfite, rubidium bisulfite, and cesium bisulfite, and mixtures thereof.

25. The fixing solution of claim 23 wherein a quantity of acetic acid, crystals of boric acid and potassium alum are substituted for said bisulfite solution.

26. The fixing solution of claim 18 wherein said first solution comprises water, a first compound selected from the group consisting of alkali metal thiocyanate, ammonium thiocyanate, alkali metal thiosulfate and ammonium thiosulfate, in a concentration range of between about to about 160 grams per liter of water, a desiccated sulfate solution selected from the group consisting of alkali metal sulfate and ammonium sulfate in a concentration range of between about 5 to about 15 grams per liter of water, a glacial acid in a concentration range of between about 20 cc to about 40 cc per liter of water wherein about every 3 parts of said glacial acetic acid has been initially diluted with 8 parts of water. crystals of boric acid having a concentration range of between about 1 gram to about 10 grams per liter of water, and potassium alum including a concentration range of between about 5 grams to about 15 grams per liter of water.

I 27. The fixing solution of claim 26 wherein said first solution comprises water, sodium thiosulfate in a concentration of about 147.5 grams per liter of water, desiccated sodium sulfate in a concentration of about 9.25 grams per liter of water, said glacial acetic acid in a concentration of about 29.2 grams per liter of water, crystals of boric acid having a concentration of about 4.62 grams per liter of water, and potassium alum having a concentration of about 9.25 grams per liter of water.

28. The fixing solution of claim 25 wherein chrome alum is substituted for said potassium alum.

29. The fixing solution of claim 24 wherein said first solution comprises water, a thiosulfate solution selected from the group consisting of alkali metal thiosulfate and ammonium thiosulfate and having a concentration in the range of between about to about l75 grams per liter of water, a desiccated sulfite solution selected from the group consisting of an alkali metal sulfite and ammonium sulfite in a concentration range of between about 4 to about 9 grams per liter of water, and a bisulfite solution selected from the group consisting of alkali metal bisulfite and ammonium bisulfite in 3,854,947 13 14 a concentration range of between about 12 to about 21 cated sodium sulfite in a concentration of about 6.6 grams per liter of water.

30. The fixing solution of claim 29 wherein said first solution comprises water, sodium thiosulfate in a concentranon of about grams per hter of water centration of about 160 grams per liter of water, desicgrams per liter of water, and sodium bisulfite in a con- UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 5,85 9h7 Dated December 17, 197

Inventor (5) Edward R It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 5, line 28, delete "by" and insert therefor be Column 7, line 51, delete "Sulfate" and insert therefor Sulfite line 66, delete "as" and insert therefor at Column 10, line 63, delete "5" and insert therefor l5 Signed and sealed this 18th day of I-Iarch 1975.

(SEAL) Attest:

C I-IARSHAL-L DANE-*2 RUTH C. 21 .30}? Commissioner of Patents Attesting Officer and Trademarks )RM FO-IOSO (10-69) uscoMM-oc 60376-P69 U.S. GOVERNMENT PRINTING OFFICE: 869. 930 

1. A RAPID PROCESS FOR PRODUCING A STABLE VISIBLE IMAGE IN A PHOTOGRAPHIC SILVER HALIDE EMULSION LAYER CONTAINING A LATENT IMAGE, A. DEVELOPING SAID LAYER IN A PHOTOGRAPHIC SILVER HALIDE DEVELOPING SOLUTION, B. FIXING SAID SILVER HALIDE FORMING THE RESULTANT IMAGE BY IMMERSING SAID LAYER IN A FIXING SOLUTION HAVING A MAJOR PORPORTION OF, (1) A FIRST SOLUTION COMPRISING A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL THIOCYANATE, AMMONIUM THIOCYANATE, ALKALI METAL THIOSULFATE AND AMMONIUM THIOSULFATE, AND, (2) A MINOR PROPORTION OF A SECOND SOLUTION INCLUDING AN ANIONIC SYNTHETIC DETERGENT HAVING A CARBON CHAIN LENGTH IN THE RANGE OF ABOUT 7 TO ABOUT 18 CARBON ATOMS PER MOLECULE AND SELECTED FROM THE GROUP CONSISTING OF AMMONIUM LAURYL SULFATE, SODIUM LAURYL SULFATE, POTASSIUM LAURYL SULFATE, ALKYLATED AROMATIC SULFONIC ACIDS, AND MIXTURES THEREOF, AND A WATER SOFTENING AGENT SELECTED FROM THE GROUP CONSISTING OF SODIUM HEXAMETAPHOSPHATE, SODIUM PYROPHOSPHATE, SODIUM TETRAPHOSPHATE, AND MIXTURES THEREOF, WHEREIN SAID SECOND SOLUTION AND SAID FIRST SOLUTION ARE MIXED AT A RATIO OF BETWEEN ABOUT 1 OUNCE TO ABOUT 20 OUNCES OF SAID SECOND SOLUTION TO ABOUT 1 GALLON OF SAID FIRST SOLUTION, AND C. RINSING THE RESULTANT IMAGE LAYER IN A MOVING WATER BATH.
 2. The rapid process of claim 1 additionally including immersing said layer in a developing stop solution after developing and pRior to said fixing.
 3. The rapid process of claim 1 wherein said second solution additionally includes a print flattening agent selected from the group consisting of propylene glycol, hexylene glycol, ethylene glycol, glycerol, and mixtures thereof, and a defoaming agent selected from the group consisting of methylhexacarbonyl, sulfonated oils, sulfonated silicones, and mixtures thereof.
 4. The rapid process of claim 1 wherein said anionic synthetic detergent includes a concentration between about 0.002 to about 0.02 grams per liter, and said water softening agent includes a concentration in the range of between about 0.01 to about 0.15 grams per liter.
 5. The rapid process of claim 3 wherein said print flattening agent includes a concentration between about 2.6 X 10 6 to about 65 X 10 6 gram moles per liter, and said defoaming agent includes a concentration range of between about 0.7 X 10 6 to about 23 X 10 6 gram mole per liter.
 6. The rapid process of claim 1 wherein said immersing of said layer in said fixing solution is between about 1 minute to about 5 minutes, and said rinsing of said resultant image in a moving water bath is between about 2 minutes to about 20 minutes.
 7. The rapid process of claim 1 wherein said alkali metal thiocyanate is selected from the group consisting of lithium thiocyanate, sodium thiocyanate potassium thiocyanate, rubidium thiocyanate, and cesium thiocyanate and said alkali metal thiosulfate is selected from the group lithium thiosulfate, sodium thiosulfate, potassium thiosulfate, rubidium thiosulfate, and cesium thiosulfate.
 8. The rapid process of claim 2 wherein said developing stop solution is a dilute solution of acetic acid including approximately between about 0.2% to about 0.8% of acetic acid, and said immersing of said layer is from between about 15 seconds to about 45 seconds.
 9. The rapid process of claim 2 wherein said developing stop solution is of the composition of said second solution and said immersing of said layer in said developing stop solution is from between about 15 seconds to about 45 seconds.
 10. The rapid process of claim 7 wherein said first solution additionally includes desiccated alkali metal sulfite, alkali metal bisulfite and water.
 11. The rapid process of claim 10 wherein said desiccated alkali metal sulfite is selected from the group consisting of lithium sulfite, sodium sulfite, potassium sulfite, rubidium sulfite, and cesium sulfite and mixtures thereof, and said alkali metal bisulfite is selected from the group consisting of lithium bisulfite, sodium bisulfite, potassium bisulfite, rubidium bisulfite and cesium bisulfite, and mixtures thereof.
 12. The rapid process of claim 11 wherein a quantity of acetic acid, crystals of boric acid and potassium alum are substituted for said alkali metal bisulfite.
 13. The rapid process of claim 1 wherein said first solution comprises water, between about 135 to about 160 grams per liter of water of a thiosulfate solution selected from the group consisting of alkali metal thiosulfate and ammonium thiosulfate, and a desiccated sulfite solution selected from the group consisting of alkali metal sulfite and ammonium sulfite having a concentration in the range of between about 5 to about 15 grams per liter of water, a glacial acetic acid in a concentration range of between about 20 cc to about 40 cc per liter of water wherein every three parts of said glacial acetic acid has been initially diluted with eight parts of water, crystals of boric acid having a concentration range of between about 1 gram to about 10 grams per liter of water, and potassium alum including a concentration range of between about 5 grams to about 15 grams per liter of water.
 14. The rapid process of claim 3 wherein said first solution comprIses water, about 147.5 grams of sodium thiosulfate per liter of water, desiccated sodium sulfite in a concentration of about 9.25 grams per liter of water, said glacial acetic acid having a concentration of about 29.2 grams per liter of water, said crystals of boric acid having a concentration of about 4.62 grams per liter of water, and said potassium alum having a concentration of about 9.25 grams per liter of water.
 15. The rapid process of claim 12 wherein chrome alum is substituted for said potassium alum.
 16. The rapid process of claim 10 wherein said first solution comprises water, a thiosulfate solution selected from the group consisting of alkali metal thiosulfate and ammonium thiosulfate and in a concentration range of between about 145 to about 175 grams per liter, a desiccated sulfite solution selected from the group consisting of an alkali metal sulfite and ammonium sulfite and in a concentration range of between about 4 to about 9 grams per liter of water, and a bisulfite solution selected from the group consisting of an alkali metal bisulfite and ammonium bisulfite in a concentration range of between about 12 to about 21 grams per liter of water.
 17. The rapid process of claim 16 wherein said first solution comprises water, sodium thiosulfate in a concentration of about 160 grams per liter of water, desiccated sodium sulfite in a concentration of about 616 grams per liter of water, and sodium bisulfite having a concentration of about 16.7 grams per liter of water.
 18. A FIXING SOLUTION FOR FIXING A STABLE VISIBLE IMAGE ON A DEVELOPED PHOTOGRAPHIC SILVER HALIDE EMULSION LAYER, COMPRISING: KNOWN SOLUTION; RESULTANT A. A MAJOR PROPORTION OF A FIRST SOLUTION INCLUDING A FIRST COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL THIOCYANATE, AMMONIUM THIOCYANATE, ALKALI METAL THIOSULATE AND AMMONIUM THIOSULFATE, AND B. A MINOR PROPORTION OF A SECOND SOLUTION INCLUDING AN ANIONIC SYNTHETIC DETERGENT HAVING A CARBON CHAIN LENGTH IN THE RANGE OF BETWEEN ABOUT 7 TO ABOUT 18 CARBON ATOMS PER MOLECULE AND SELECTED FROM THE GROUP CONSISTING OF AMMONIUM LAURYL SULFATE, SODIUM LAURYL SULFATE, AND POTASSIUM LAURYL SULFATE, ALKYLATED AROMATIC SULFONIC ACIDS, AND MIXTURES THEREOF, AND A WATER SOFTENING AGENT SELECTED FROM SODIUM HEXAMETAPHOSPHATE, SODIUM PYROPHOSPHATE, SODIUM TETRAPHOSPHATE, AND MIXTURES THEREOF, WHEREIN SAID SECOND SOLUTION AND SAID FIRST SOLUTION ARE MIXED AT A RATIO BETWEEN ABOUT 1 OUNCE TO ABOUT 20 OUNCES OF SAID SECOND SOLUTION TO ABOUT 1 GALLON OF SAID FIRST SOLUTION.
 19. The fixing solution of claim 18 wherein said second solution additionally includes a print flattening agent selected from the group consisting of propylene glycol, hexylene glycol, ethylene glycol, glycerol, and mixtures thereof, and a defoaming agent selected from the group consisting of methylhexacarbonyl, sulfonated oils, sulfonated silicones and mixtures thereof.
 20. A fixing solution of claim 18 wherein said anionic synthetic detergent includes a concentration in the range of between about 0.002 to about 0.02 grams per liter, and said water softening agent includes a concentration in the range of between about 0.01 to about 0.15 grams per liter.
 21. The fixing solution of claim 19 wherein said print flattening agent includes a concentration in the range of between about 2.6 X 10 6 to about 65 X 10 6 gram moles per liter, and said defoaming agent includes a concentration in the range of about 0.7 X 10 6 to about 23 X 10 6 gram moles per liter.
 22. The fixing solution of claim 18 wherein said alkali metal thiocyanate is selected from the group consisting of lithium thiocyanate, sodium thiocyanate, potassium thiocyanate, rubidium thiocyanate, and cesium thiocyanate, and mixtures thereof, and said alkali metal thiosulfate is selected from the group consistiNg of lithium thiosulfate, sodium thiosulfate, potassium thiosulfate, rubidium thiosulfate and cesium thiosulfate, and mixtures thereof.
 23. The fixing solution of claim 22 wherein said first solution additionally includes a desiccated sulfite solution selected from the group consisting of an alkali metal sulfite and ammonium sulfite, and a bisulfite solution selected from the group consisting of an alkali metal bisulfite and ammonium bisulfite.
 24. The fixing solution of claim 23 wherein said desiccated alkali metal sulfite is selected from the group consisting of lithium sulfite, sodium sulfite, potassium sulfite, rubidium sulfite and cesium sulfite and mixtures thereof, and said alkali metal bisulfite is selected from the group consisting of lithium bisulfite, sodium bisulfite, potassium bisulfite, rubidium bisulfite, and cesium bisulfite, and mixtures thereof.
 25. The fixing solution of claim 23 wherein a quantity of acetic acid, crystals of boric acid and potassium alum are substituted for said bisulfite solution.
 26. The fixing solution of claim 18 wherein said first solution comprises water, a first compound selected from the group consisting of alkali metal thiocyanate, ammonium thiocyanate, alkali metal thiosulfate and ammonium thiosulfate, in a concentration range of between about 135 to about 160 grams per liter of water, a desiccated sulfate solution selected from the group consisting of alkali metal sulfate and ammonium sulfate in a concentration range of between about 5 to about 15 grams per liter of water, a glacial acid in a concentration range of between about 20 cc to about 40 cc per liter of water wherein about every 3 parts of said glacial acetic acid has been initially diluted with 8 parts of water, crystals of boric acid having a concentration range of between about 1 gram to about 10 grams per liter of water, and potassium alum including a concentration range of between about 5 grams to about 15 grams per liter of water.
 27. The fixing solution of claim 26 wherein said first solution comprises water, sodium thiosulfate in a concentration of about 147.5 grams per liter of water, desiccated sodium sulfate in a concentration of about 9.25 grams per liter of water, said glacial acetic acid in a concentration of about 29.2 grams per liter of water, crystals of boric acid having a concentration of about 4.62 grams per liter of water, and potassium alum having a concentration of about 9.25 grams per liter of water.
 28. The fixing solution of claim 25 wherein chrome alum is substituted for said potassium alum.
 29. The fixing solution of claim 24 wherein said first solution comprises water, a thiosulfate solution selected from the group consisting of alkali metal thiosulfate and ammonium thiosulfate and having a concentration in the range of between about 145 to about 175 grams per liter of water, a desiccated sulfite solution selected from the group consisting of an alkali metal sulfite and ammonium sulfite in a concentration range of between about 4 to about 9 grams per liter of water, and a bisulfite solution selected from the group consisting of alkali metal bisulfite and ammonium bisulfite in a concentration range of between about 12 to about 21 grams per liter of water.
 30. The fixing solution of claim 29 wherein said first solution comprises water, sodium thiosulfate in a concentration of about 160 grams per liter of water, desiccated sodium sulfite in a concentration of about 6.6 grams per liter of water, and sodium bisulfite in a concentration of about 16.7 grams per liter of water. 